Preparation of 1,1&#39;-peroxydicyclohexylamine

ABSTRACT

The caprolactam intermediate, 1,1&#39;&#39;-peroxydicyclohexylamine, can be prepared by reacting cyclohexanone, with an aliphatic or alicyclic hydroperoxide and ammonia. In addition to the hexylamine intermediate, there is also formed as a by-product tbutyl alcohol.

United States Patent 11 1 Turner Aug. 19, 1975 1 PREPARATION OF 1,1-PEROXYDlCYCLOHEXYLAMINE [75] Inventor: John O. Turner, West Chester,Pa.

[73] Assignee: Sun Research and Development (10.,

Philadelphia, Pa.

221 Filed: Jan. 2, 1973 21 Appl. No.: 320,225

OTHER PUBLICATIONS Hawkins J. Chem. Soc. (C) 1969, 2678-2681.

Hawkins .1. Chem. Soc. (C) 1969, 2682-2686.

Primar E.\'aminer-Raymond V. Rush Attorney, Agent, or Firm-George L.Church; Donald R. Johnson; Stanford M. Back 5 7 ABSTRACT The caprolactamintermediate, 1,1 -peroxydicyclohexylamine, can be prepared by reactingcyclohexanone, with an aliphatic or alicyclic hydroperoxide and ammonia.In addition to the hexylamine intermediate, there is also formed as aby-product t-butyl alcohol.

6 Claims, No Drawings PREPARATION OF 1,1' PEROXYDICYCLOHEXYLAMINE Thisinvention relates to a process for the preparation of a caprolactamintermediate,.More particularly, this invention relates,to an improvedprocess for the production of. 1 ,1'-peroxydicyclohexylamine hereafterhexylamine) by reacting together cyclohexanone, an aliphatic oralicyclic hydroperoxide, and ammonia.

Hawkins er al, J. Chem. sof 'j, "2663 1969) teach the preparation of the'hexy lamine intermediate, .using cyclohexanone, hydrogen peroxide, andammonia. This method, while effective, is characterized by the use ofthe expensive reagent, hydrogen peroxide, which isdifficult to handle inlarge amounts.

Hawkins et al, US. Pat. No. 3,575,964 also teach the conversion of thehexylamine compound to caprolactam and cyclohexanone by heating thehexylamine with lithium chloride or a strong base at about 100C.

Finally, Hawkins et al., J. Chem, Soc., 2682 (1969) report the reactionof cyclohexanone, tbutylhydroperoxide, and ammonia to yieldt-butylperoxycyclohexylamine rather than the SUMMARY OF THE INVENTIONThus, the present process provides a process for the preparation of 1,1-peroxydicyclohexylamine by contacting cyclohexanone with an aliphaticor alicyclic hydroperoxide and ammonia in the presence of an acceleratorfor the reaction, such as NH NO in accordance with the followingreaction scheme:

Accelerator 2 ROOH NH O--O ROH H O where R is an aliphatic or alicyclichydrocarbon moiety.

DESCRIPTION OF THE INVENTION The hydroperoxide reactant is any primary,secondary or tertiary aliphatic or alicyclic hydroperoxide, preferablyan alkyl or cycloalkyl hydroperoxide, having from 3 to 12 carbon atoms.Included amongst these are such compounds as n-butylhydroperoxide,tbutylhydroperoxide, 2-pentylhydroperoxide, t-pentylhydroperoxide,isooctylhydroperoxide, cyclopentylhy- .cyclohexylhydroperoxide,

2 1 methylcyclopentylhydroperoxide,

l-methylcyclohexylhydroperoxide, and the like. Of these,cyclohexylhydroperoxide is preferred inasmuch as the correspond:ing-cyclohexyl alcohol formed as ,a by-product from this hydroperoxidemay readily be oxidized to thecorrespondingcyclohexanone and recycled'to the reaction medium.

The reaction is conveniently conducted by contacting a mixture of thecyclohexanone and desired hydroperoxide dissolved ina suitable organicsolvent with a molar excess of ammonia which is added to'the reactionmixture as a liquid at low temperatures. The reaction is desirablycarried out at a temperature of from about l0 to 50C, and. preferablyfrom about 0 to 20C for about 6 to 12 hours. It is preferred, althoughnot essential, that an accelerator for the reaction be employed, i.e. acompound such as NH NO or the like in amounts of about 1 to 12 grams per35 grams of cyclohexanone. If desired, small amounts of a stabilizer forthe hydroperoxide such as the sodium salt of ethylenediaminetetraaceticacid, or the like may be employed, although this is not essential. Theorganic solvents which may be used include C C alcohols, i.e. alkanolssuch as ethyl or propyl alcohol, and the like.

The mole ratio of hydroperoxide to cyclohexanone droperoxide,

should desirably be maintained at stoichiometric quantities, i.e. at aratio of about 05:10, while the mole ratio of ammonia to cyclohexanoneshould be in the range of about 0.5 to 10.0:l.0, and preferably at least2:1 in order to maintain an excess of ammonia.

The hexylamine product is readily recovered by con ventional means knownin the art, as for example by distillation or ether extraction, orcombinations thereof.

The process of this invention will now be illustrated by the followingexamples.

EXAMPLE 1 Into a flask is added 35.0 gms. of cyclohexanone, 50.0 gms. oft-butylhydroperoxide, 50 cc of ethyl alcohol, 0.5 gms. ofethylenediaminetetraacetic acid.- disodium salt, 10.0 gms. of NI-I NOand 60.0 gms. of NH;,. The reaction is stirred at 0 for 18 hours. Whenthe reaction is complete the mixture is extracted with ether. The etherextract is then worked up by distillation and yields, along with someunreacted starting materials, 1,1'-peroxydicyclohexylamine and t-butylalcohol.

EXAMPLE 2 In accordance with the procedures of Example 1, 35.0 gms. ofcyclohexanone, 50.0 gms. of percent t-butylhydroperoxide, 70.0 gms. ofNH in 50 cc of ethanol is reacted at 0C for 18 hours. No stabilizer oraccelerator is employed. The product is worked up as in Example 1 andyields the hexylamine and t-butyl alcohol.

EXAMPLE 3 The process of Example 1 is repeated, except thatcyclohexylhydroperoxide is substituted for tbutylhydroperoxide. Theproduct again is l,1-peroxydicyclohexylamine, together with somecyclohexy] alcohol.

What is claimed is:

1. A process for the production and recovery of1,1-peroxydicyclohexylamine and an aliphatic or alicyclic alcohol, whichcomprises reacting at a temperature of from C to 50C cyclohexanone andammonia with a hydroperoxide of the formula ROOH, wherein R is aprimary, secondary, or tertiary alkyl or cycloalkyl hydrocarbon grouphaving from 3 to 12 carbon atoms, and recovering from the reactionmixture said l,l'-peroxydicyclohexylamine and an alcohol of the formulaROH, wherein R is defined as above, and wherein the mole ratio ofhydroperoxide to cyclohexanone is about 0.5:1.0.

2. The process according to claim 1 wherein NH NO compound is used as areaction accelerator.

1. A PROCESS FOR THE PRODUCTION AND RECOVERY OF 1,1''-PEROXYDICYCLOHEXYLAMINE AND AN ALIPHATIC OR ALICYCLIC ALCOHOL, WHICHCOMPRISES REACTING AT A TEMPERATURE F FROM -10*C TO 50*C CYCLOHEXANONEAND AMMONIA WITH A HYDROPEROXIDE OF THE FORMULA ROOH, WHEREIN R IS APRIMARY, SECONDARY, OR TERTIARY ALKYL OR CYCLOALKYL HYDROCARBON GROUPHAVING FROM 3 TO 12 CARBON ATOMS, AND RECOVERING FROM THE REACTIONMIXTUE SAID 1,1'' -PEROXYDICYCLOHEXYLAMINE AND AN ALCOHOL OF THE FORMULAROH, WHEREIN R IS DEFINED AS ABOVE, AN WHEREIN THE MOLE RATIO OFHYDROPEROXIDE TO CYCLOHEXANONE IS ABOUT 0.5:10.
 2. The process accordingto claim 1 wherein NH4NO3 compound is used as a reaction accelerator. 3.The process according to claim 1 wherein the reaction is carried out inthe presence of a suitable organic solvent.
 4. The process according toclaim 1 wherein the hydroperoxide is cyclohexylhydroperoxide and thealcohol recovered is cyclohexyl alcohol.
 5. The process according toclaim 1 wherein the hydroperoxide is t-butylhydroperoxide and thealcohol recovered is t-butyl alcohol.
 6. The process according to claim1 wherein the mole ratio of ammonia to cyclohexanone is about 0.5 to10.0:1.0.